JP4908858B2 - Method for producing fine carbon fiber aggregate - Google Patents
Method for producing fine carbon fiber aggregate Download PDFInfo
- Publication number
- JP4908858B2 JP4908858B2 JP2006021873A JP2006021873A JP4908858B2 JP 4908858 B2 JP4908858 B2 JP 4908858B2 JP 2006021873 A JP2006021873 A JP 2006021873A JP 2006021873 A JP2006021873 A JP 2006021873A JP 4908858 B2 JP4908858 B2 JP 4908858B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fine carbon
- component
- fiber aggregate
- aggregate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1276—Aromatics, e.g. toluene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
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Description
本発明は、コーティング材料等の電気特性、熱特性等の物理特性向上に適した添加剤として有用な微細炭素繊維集合体の製造方法、及びこの製造方法で得られた微細炭素繊維集合体を含有するコーティング材料に関する。 The present invention includes a method for producing a fine carbon fiber aggregate useful as an additive suitable for improving physical properties such as electrical properties and thermal properties of a coating material, and the fine carbon fiber aggregate obtained by this production method. It relates to a coating material.
微細炭素繊維を製造する方法として、ベンゼン、トルエン又はキシレン等の炭素源となる炭化水素を気相中で熱分解する気相成長法が知られている。例えば、熱分解帯域に置かれた基板上に金属微粒子を散布し、そこから微細炭素繊維を成長させる基板法、浮遊する金属微粒子を触媒として微細炭素繊維を生成させる浮遊法などである。この気相成長法で得られる微細炭素繊維は、有機材料、無機材料及び金属材料等の母材の性能向上及び新規機能を発現させる添加物として期待されている。 As a method for producing fine carbon fibers, a vapor phase growth method is known in which hydrocarbons serving as a carbon source such as benzene, toluene or xylene are thermally decomposed in a gas phase. For example, there are a substrate method in which metal fine particles are dispersed on a substrate placed in a thermal decomposition zone and fine carbon fibers are grown therefrom, and a floating method in which fine carbon fibers are generated using floating metal fine particles as a catalyst. The fine carbon fiber obtained by this vapor phase growth method is expected as an additive for improving the performance of a base material such as an organic material, an inorganic material, and a metal material and exhibiting a new function.
しかし、この気相成長法により得られる微細炭素繊維は、非常に大きなアスペクト比を有し、また、微細炭素繊維同士の間にファンデルワールス力が働く。このため、製造された微細炭素繊維は、相互に密に絡み合った凝集状態で生成される(特許文献1及び特許文献2)。 However, the fine carbon fiber obtained by this vapor growth method has a very large aspect ratio, and van der Waals force acts between the fine carbon fibers. For this reason, the manufactured fine carbon fiber is produced | generated in the aggregation state intertwined closely (patent document 1 and patent document 2).
例えば、基板法により得られる微細炭素繊維は、微細炭素繊維同士が互いに絡み合い粒状の凝集状態を形成している。また、浮遊法により得られる微細炭素繊維に関しても、絡み合いが生じる。凝集した微細炭素繊維を使用すると、樹脂等のマトリックス中において炭素繊維凝集体の分散が進まず、従来、凝集状態を形成した微細炭素繊維を細分化する方法が行われていた。 For example, in the fine carbon fiber obtained by the substrate method, the fine carbon fibers are entangled with each other to form a granular aggregated state. In addition, entanglement occurs with respect to the fine carbon fiber obtained by the floating method. Use of agglomerated fine carbon fibers, dispersion of the carbon fiber aggregate does not proceed in a matrix of resin or the like, traditional method for subdividing the fine carbon fibers to form aggregated state has been performed.
従来行われていた細分化方法としては、例えば特許文献1に示す振動ボールミルを使用して粉砕処理する手法、特許文献2に示すジェットミルにより粉砕する手法、特許文献3に示すボールミル、ロータースピードミル、カッティングミル、ホモジナイザー、振動ミル又はアトライタ等で機械的に粉砕する手法、並びに特許文献4に示す高速気流中衝撃処理装置を利用して高衝撃力を作用させて破断する手法などが挙げられる。 Conventional subdivision methods include, for example, a pulverizing method using a vibrating ball mill shown in Patent Document 1, a pulverizing method using a jet mill shown in Patent Document 2, a ball mill shown in Patent Document 3, and a rotor speed mill. , A method of mechanically pulverizing with a cutting mill, a homogenizer, a vibration mill, an attritor, or the like, and a method of breaking by applying a high impact force using a high-speed air-flow impact treatment device shown in Patent Document 4.
しかしながら、凝集した微細炭素繊維を粉砕して細分化する従来の手法には種々の問題点が存在する。例えば、圧壊に分類されるボールミルタイプの粉砕機では、粉砕メディアとして用いられる剛性ボールによって微細炭素繊維を押し潰し破壊しながら細分化が進行する為、微細炭素繊維自体の構造欠陥が生じ、このため、導電性等の物性が低下することとなる。また、セラミック球などの粉砕媒体を使用するとセラミック粉が発生し、このセラミック粉が不純物として細分化された微細炭素繊維に混入されることとなる。 However, there are various problems in the conventional method of pulverizing and subdividing the agglomerated fine carbon fibers. For example, in a ball mill type pulverizer classified as crushing, since the fine carbon fibers are crushed and broken by the rigid balls used as the pulverizing media, the fine carbon fibers themselves cause structural defects. The physical properties such as conductivity will be lowered. In addition, when a grinding medium such as a ceramic sphere is used, ceramic powder is generated, and this ceramic powder is mixed into the fine carbon fibers that are subdivided as impurities.
また、ジェットミルで粉砕する場合には、微細炭素繊維の表面に存在する空気の層は、粉砕時、微細炭素繊維同士の衝突、又は、壁あるいは運動体との衝突において中間に存在して衝撃を抑え、粉砕効率の低下を招くという問題があった。 Further, when pulverized with a jet mill, an air layer present on the surface of the fine carbon fibers, during pulverization, collision of the fine carbon fiber 維同 mechanic, or present in intermediate in the collision with the wall or the moving body There was a problem that the impact was suppressed and the pulverization efficiency was lowered.
本発明の目的は、優れた電気特性、熱特性、機械特性を有する、円相当メディアン径(以下、メディアン径という)が30μm未満の微細炭素集合体の繊維集合体を得る微細炭素繊維集合体の製造方法を提供することである。また、本発明の目的はそのようにして得られた微細炭素繊維集合体を含有するコーティング材料を提供することである。 An object of the present invention is to provide a fine carbon fiber aggregate that has excellent electrical characteristics, thermal characteristics, and mechanical characteristics, and obtains a fine carbon aggregate fiber aggregate having a circle equivalent median diameter (hereinafter referred to as median diameter) of less than 30 μm. It is to provide a manufacturing method. Moreover, the objective of this invention is providing the coating material containing the fine carbon fiber aggregate | assembly obtained in that way.
本発明は、(a)メディアン径が30μm以上の微細炭素繊維集合体と(b)その分散媒体(25℃で液体のもの)を含有する組成物を、加速し、乱流及び/又は衝突流を形成することで、組成物中に含まれる(a)成分にせん断力及び/又は衝撃を与えることにより、(a)成分を粉砕する工程(以下、本発明の粉砕工程という)を含む、メディアン径が30μm未満の微細炭素繊維集合体の製造方法であって、〔(a)成分を粉砕した後の微細炭素繊維集合体のID/IG〕/〔(a)成分を粉砕する前の微細炭素繊維集合体のID/IG〕(ID/IGはアルゴンレーザーの514nmにてラマン分光分析した測定値より算出)が0.7〜1.5である微細炭素繊維集合体の製造方法を提供するものである。 In the present invention, a composition containing (a) a fine carbon fiber aggregate having a median diameter of 30 μm or more and (b) a dispersion medium (liquid at 25 ° C.) is accelerated, turbulent and / or impinging. A median including a step of pulverizing the component (a) (hereinafter referred to as the pulverization step of the present invention) by applying shearing force and / or impact to the component (a) contained in the composition by forming A method for producing a fine carbon fiber aggregate having a diameter of less than 30 μm, wherein [ D D / I G of fine carbon fiber aggregate after pulverizing component (a)] / [(a) before pulverizing component The fine carbon fiber aggregate I D / I G ] (I D / I G is calculated from the measured value obtained by Raman spectroscopic analysis at 514 nm of an argon laser) is 0.7 to 1.5. A manufacturing method is provided.
更に、本発明は、この製造方法で得られた微細炭素繊維集合体と有機バインダーを含有するコーティング材料を提供するものである。 Furthermore, this invention provides the coating material containing the fine carbon fiber aggregate obtained by this manufacturing method, and an organic binder.
本発明において、「微細炭素繊維集合体」とは外径が500nm以下の炭素繊維の集合体をいい、また、「メディアン径が30μm以上の微細炭素繊維集合体」は、例えば、微細炭素繊維集合体の合成後において得られる微細炭素繊維集合体であり、好ましくは、合成後に所定繊維集合体長とするために気流粉砕を施した後に得られた、メディアン径が30μm以上の微細炭素繊維集合体である。なお、特に限定されるものではないが、このメディアン径が30μm以上の微細炭素繊維集合体は、好ましくはメディアン径が30〜200μm、より好ましくは30〜100μm程度のものである。 In the present invention, “fine carbon fiber aggregate” refers to an aggregate of carbon fibers having an outer diameter of 500 nm or less, and “fine carbon fiber aggregate having a median diameter of 30 μm or more” is, for example, a fine carbon fiber aggregate. It is a fine carbon fiber aggregate obtained after the synthesis of the body, preferably a fine carbon fiber aggregate having a median diameter of 30 μm or more obtained after subjecting to airflow pulverization to obtain a predetermined fiber aggregate length after synthesis. is there. Although not particularly limited, the fine carbon fiber aggregate having a median diameter of 30 μm or more preferably has a median diameter of 30 to 200 μm, more preferably about 30 to 100 μm.
ここでメディアン径とは、画像解析装置(例えば、シスメックス株式会社製FPIA3000)にて各微細炭素繊維集合体の輪郭内の面積を求め、各微細炭素繊維集合体の円相当径を計算し、個数基準でメディアン径として数値化したものである。 Here, the median diameter is obtained by calculating the area within the outline of each fine carbon fiber aggregate with an image analysis device (for example, FPIA 3000 manufactured by Sysmex Corporation), calculating the equivalent circle diameter of each fine carbon fiber aggregate, This is a numerical value based on the median diameter.
本発明によれば、微細炭素繊維集合体の導電性等の特徴的物性を著しく低下させることなく、粉砕された微細炭素繊維集合体を得ることができる。また、この製造方法で得られた微細炭素繊維集合体を導電コーティング材料の成分として使用すれば、塗膜中に微細炭素繊維集合体に起因する凝集体がなく、外観が良好な導電膜を得ることができる。 According to the present invention, a pulverized fine carbon fiber aggregate can be obtained without significantly reducing characteristic properties such as conductivity of the fine carbon fiber aggregate. Moreover, if the fine carbon fiber aggregate obtained by this production method is used as a component of the conductive coating material, a conductive film having a good appearance without an aggregate resulting from the fine carbon fiber aggregate in the coating film is obtained. be able to.
以下、本発明を実施形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on embodiments.
本発明において、(a)メディアン径が30μm以上の微細炭素繊維集合体と(b)その分散媒体(25℃で液体)を含有する組成物を加速し、乱流及び/又は衝突流を形成することで、好ましくは剛性ビーズ等の分散メディア同士の衝突及び/又は摩擦によることなく、組成物中に含まれる(a)成分にせん断力及び/又は衝撃を与える方法として、例えば、つぎの方法を好ましく例示できる。
〔粉砕方法1〕
本発明の粉砕方法の一実施態様として、(a)成分と(b)成分の混合物を、回転する回転ロータと固定ステータとの間隙を通過させることにより、(a)成分と(b)成分の混合物にせん断力及び/又は衝撃を与える方法が挙げられる。このような方法においては、例えば、図5に示すように、比較的高速にて回転されるロータ1とステータ2との回転数の違いにより、ロータとステータの間のギャップ3において、高いせん断力と乱流エネルギーが与えられ、このギャップを通過する流体((a)成分と(b)成分を含有する組成物)中に含まれる(a)成分が粉砕されるものである。(a)成分はメディアン径が30μm未満に粉砕されるが、好ましくは30μm未満、より好ましくは20μm未満、最も好ましくは10μm未満に粉砕される。
In the present invention, a composition containing (a) a fine carbon fiber aggregate having a median diameter of 30 μm or more and (b) a dispersion medium (liquid at 25 ° C.) is accelerated to form a turbulent flow and / or a collision flow. Thus, preferably, as a method of applying a shearing force and / or impact to the component (a) contained in the composition without causing collision and / or friction between dispersion media such as rigid beads, the following method is used, for example. Preferred examples can be given.
[Crushing method 1]
As one embodiment of the pulverization method of the present invention, the mixture of the component (a) and the component (b) is passed through the gap between the rotating rotor and the stationary stator so that the components (a) and (b) The method of giving a shear force and / or an impact to a mixture is mentioned. In such a method, for example, as shown in FIG. 5, a high shear force is generated in the gap 3 between the rotor and the stator due to the difference in the rotational speed between the rotor 1 and the stator 2 that are rotated at a relatively high speed. The component (a) contained in the fluid (the composition containing the component (a) and the component (b)) passing through the gap is pulverized. The component (a) is pulverized to a median diameter of less than 30 μm, preferably pulverized to less than 30 μm, more preferably less than 20 μm, and most preferably less than 10 μm.
この粉砕方法によれば、粉砕における微細炭素繊維集合体の損傷が少ないか、又は殆どないので、〔(a)成分を粉砕した後の微細炭素繊維集合体のID/IG〕/〔(a)成分を粉砕する前の微細炭素繊維集合体のID/IG〕が0.7〜1.5、好ましくは0.8〜1.4、より好ましくは0.9〜1.3の、(a)成分が粉砕された微細炭素繊維集合体を得ることができる。 According to this pulverization method, there is little or almost no damage to the fine carbon fiber aggregates during the pulverization. Therefore, [I D / I G ] of the fine carbon fiber aggregates after pulverizing the component (a) / [( a) I D / I G of the fine carbon fiber aggregate before pulverizing the component is 0.7 to 1.5, preferably 0.8 to 1.4, more preferably 0.9 to 1.3. , (A) A fine carbon fiber aggregate in which the component is pulverized can be obtained.
このような方法を実施する装置としては、ロータ−ステータ式の高せん断インラインミキサーなどがあり、具体的には例えば、キャビトロン(商標名、(株)ユーロテック製)、マグネトロン(MAGNETRON、KINEMATIKA AG製)、YTRON-Z(YTRON製)、インラインミキサDR(IKA製)、インラインミキサDRS(IKA製)、インライン型ミキサー(SILVERSN製)などが例示される。 As an apparatus for carrying out such a method, there is a rotor-stator type high shear in-line mixer. Specifically, for example, Cavitron (trade name, manufactured by Eurotech Co., Ltd.), Magnetron (MAGNETRON, manufactured by KINEMATIKA AG) ), YTRON-Z (manufactured by YTRON), in-line mixer DR (manufactured by IKA), in-line mixer DRS (manufactured by IKA), in-line mixer (manufactured by SILVERSN) and the like.
この場合において、(b)成分として使用される、メディアン径が30μm以上の微細炭素繊維集合体に対する分散媒体としては、微細炭素繊維集合体に対し安定で、粉砕処理温度、例えば25℃において液状のものであれば、特に限定されるものではなく、例えば、アルコール類(多価アルコールを含む)、エーテル類、ケトン類、エステル類、芳香族溶媒、炭化水素溶媒、水あるいはこれらの混合物などを用いることが可能であるが、微細炭素繊維集合体に対して良好な分散特性を有し、かつ粉砕処理後において、容易に揮発、洗浄等によって除去可能なものが好ましく、低揮発性の水溶性媒体、例えば、炭素数1〜5の1価アルコールが好ましく、この中でも、エタノール、イソプロパノールが特に好ましい。 In this case, the dispersion medium for the fine carbon fiber aggregate used as the component (b) having a median diameter of 30 μm or more is stable to the fine carbon fiber aggregate and is liquid at a pulverization temperature, for example, 25 ° C. If it is a thing, it will not specifically limit, For example, alcohol (including polyhydric alcohol), ethers, ketones, esters, an aromatic solvent, a hydrocarbon solvent, water, or these mixtures are used. However, it is preferable to use a low-volatile water-soluble medium that has good dispersion characteristics with respect to the fine carbon fiber aggregate and can be easily removed by volatilization, washing, etc. after pulverization. For example, a monohydric alcohol having 1 to 5 carbon atoms is preferable, and among these, ethanol and isopropanol are particularly preferable.
さらに、(a)成分と(b)成分を含有する組成物には、必要に応じて、(a)成分の分散剤を使用することが好ましい。このような分散剤として、例えばエチレンオキシド・プロピレンオキシドブロック共重合体が使用される。 Furthermore, in the composition containing the component (a) and the component (b), it is preferable to use a dispersant of the component (a) as necessary. As such a dispersant, for example, an ethylene oxide / propylene oxide block copolymer is used.
粉砕方法1に供される組成物中、(a)成分の含有量は、微細炭素繊維集合体の生産性、及び粉砕効率の観点より、好ましくは0.1〜10質量%であり、より好ましくは0.1〜5質量%である。また、この粉砕方法1に供される組成物の粘度としては、例えば、1〜10,000cps、より好ましくは1〜3,000cps程度であることが粉砕効率の上から望ましい。なお、この粘度は、粉砕処理温度における粘度が上記範囲にあれば良いが、一般的には常温(25℃±5℃)域における粘度である。 In the composition is subjected to grinding method 1, the content of component (a), the productivity of the fine carbon fiber aggregate, and Ri by the viewpoint of grinding efficiency, good Mashiku is 0.1 to 10 mass% More preferably, it is 0.1-5 mass%. Moreover, as a viscosity of the composition used for this grinding | pulverization method 1, it is desirable from a viewpoint of grinding | pulverization efficiency that it is about 1-10,000 cps, for example, More preferably, it is about 1-3000 cps. In addition, although this viscosity should just be in the said range at the grinding | pulverization processing temperature, generally it is a viscosity in normal temperature (25 degreeC +/- 5 degreeC) area | region.
また、粉砕方法1に供される組成物中に、必要に応じて添加される分散剤の含有量は、好ましくは0.1〜10質量%である。 Further, the content of the dispersant added as necessary in the composition to be subjected to the pulverization method 1 is preferably 0.1 to 10% by mass.
なお、特に限定されるものではなく、使用する装置におけるロータとステータの形状、構成等によっても左右されるが、回転ローターの周速は例えば10〜50m/秒で運転され、また、ロータとステータとの間のキャップ間距離は、30μm〜0.5mm程度とされる。 The rotational speed of the rotating rotor is operated at, for example, 10 to 50 m / sec, although it is not particularly limited and depends on the shape and configuration of the rotor and stator in the apparatus used. The distance between the caps is about 30 μm to 0.5 mm.
また、粉砕方法1における回転ロータとステータの開口部頻度(チャンバーの圧縮〜開放の回数)は、好ましくは1〜5MHzである。
〔粉砕方法2〕
本発明の粉砕方法の他の一実施態様として、(a)成分と(b)成分を含有する組成物同士を対向衝突させる方法が挙げられる。例えば、当該組成物を加圧した後、チャンバー内で2つに分け、図6に示すように対向するノズル4,4へと導いて加速後、噴出させ、チャンバー中央部5にて対向衝突させて、(a)成分を粉砕後、導出ライン6によって排出することによって行われる。
Further, the frequency of opening portions of the rotating rotor and the stator in the pulverization method 1 (the number of times the chamber is compressed to opened) is preferably 1 to 5 MHz.
[Crushing method 2]
Another embodiment of the pulverization method of the present invention includes a method in which the compositions containing the component (a) and the component (b) collide with each other. For example, after pressurizing the composition, it is divided into two in the chamber, guided to the opposing nozzles 4 and 4 as shown in FIG. Then, after the component (a) is pulverized, it is discharged by the discharge line 6.
(a)成分はメディアン径が30μm未満に粉砕されるが、好ましくは30μm未満、より好ましくは20μm未満、最も好ましくは10μm未満に粉砕される。 The component (a) is pulverized to a median diameter of less than 30 μm, preferably pulverized to less than 30 μm, more preferably less than 20 μm, and most preferably less than 10 μm.
この粉砕方法によれば、粉砕における微細炭素繊維集合体の損傷が少ないか、又は殆どないので、〔(a)成分を粉砕した後の微細炭素繊維集合体のID/IG〕/〔(a)成分を粉砕する前の微細炭素繊維集合体のID/IG〕が0.7〜1.5、好ましくは0.8〜1.4、より好ましくは0.9〜1.3の、(a)成分が粉砕された微細炭素繊維集合体を得ることができる。 According to this pulverization method, there is little or almost no damage to the fine carbon fiber aggregates during the pulverization. Therefore, [I D / I G ] of the fine carbon fiber aggregates after pulverizing the component (a) / [( a) I D / I G of the fine carbon fiber aggregate before pulverizing the component is 0.7 to 1.5, preferably 0.8 to 1.4, more preferably 0.9 to 1.3. , (A) A fine carbon fiber aggregate in which the component is pulverized can be obtained.
このような方法を実施する装置としては、高圧にて対向流を衝突させる湿式ジェットミル、具体的には、例えば、アルティマイザー(商標名、(株)スギノマシン製)、ナノマイザー(商標名、吉田興業(株))、マイクロフルイダイザー(商標名、みづほ工業(株))が例示される。この場合において、(b)成分として使用される、メディアン径が30μm以上の微細炭素繊維集合体の分散媒体及び分散剤、並びに粉砕方法2に供される組成物中のそれぞれの含有量、組成物の粘度等は粉砕方法1に記載したものと同様のものとすることができる。 As an apparatus for carrying out such a method, a wet jet mill that collides a counter flow at a high pressure, specifically, for example, an optimizer (trade name, manufactured by Sugino Machine Co., Ltd.), a nanomizer (trade name, Yoshida). Kogyo Co., Ltd.) and Microfluidizer (trade name, Mizuho Industry Co., Ltd.). In this case, the fine carbon fiber aggregate dispersion medium and dispersant used as the component (b), and the content and composition of each in the composition used for the grinding method 2 The viscosity and the like can be the same as those described in the grinding method 1.
また、湿式ジェットミルにおけるノズル4,4の圧力は例えば50〜250MPa、(a)成分と(b)成分を含有する組成物の流速は300〜900m/秒程度で運転される。
〔(a)成分として好ましいもの〕
外径が500nm以下の炭素繊維集合体であれば、本発明の製造方法の(a)成分として使用され得る。この中でも、微細炭素繊維集合体は、樹脂等のマトリックス中に添加したとき、その添加量が少なくても十分な電気的特性、機械的特性、熱的特性等を発揮させるために、可能な限り微細炭素繊維を用い、さらにこれら炭素繊維が一本一本ばらばらになることなく互いに強固に結合し、疎な構造で樹脂中に保持される構造を有する炭素繊維構造体の集合体であることが好ましく、また炭素繊維自体の一本一本が極力欠陥の少ない炭素繊維構造体の集合体であることが好ましい。
The pressure of the nozzles 4 and 4 in the wet jet mill is, for example, 50 to 250 MPa, and the flow rate of the composition containing the components (a) and (b) is operated at about 300 to 900 m / sec.
[Preferred as component (a)]
Any carbon fiber aggregate having an outer diameter of 500 nm or less can be used as the component (a) in the production method of the present invention. Among this, the fine carbon fiber aggregate, when added to the matrix such as resin, sufficient electrical characteristics even with a small amount added, the mechanical properties, in order to exhibit the thermal properties and the like, which can be using a fine carbon fiber as long, further that these carbon fibers are tightly bound to each other without being one apart one, an aggregate of carbon fibrous structure having a structure that is held by the sparse structure in the resin It is preferable that each carbon fiber itself is an aggregate of carbon fiber structures with as few defects as possible.
すなわち、本発明の粉砕方法1又は2に供される微細炭素繊維集合体として、外径15〜100nmの炭素繊維から構成される3次元ネットワーク状の構造を有する炭素繊維構造体の集合体であって、前記3次元ネットワーク状炭素繊維構造体は、前記炭素繊維が複数延出する態様で、当該炭素繊維を互いに結合する粒状部を有しており、かつ当該粒状部は前記炭素繊維の成長過程において形成されてなるものであることが好ましい。 That is, the fine carbon fiber aggregate used in the pulverization method 1 or 2 of the present invention is an aggregate of carbon fiber structures having a three-dimensional network structure composed of carbon fibers having an outer diameter of 15 to 100 nm. In addition, the three-dimensional network-like carbon fiber structure has a granular portion that couples the carbon fibers to each other in a manner in which a plurality of the carbon fibers extend, and the granular portion is a growth process of the carbon fibers. It is preferable that it is formed in.
このような炭素繊維構造体は、例えば、図3に示すSEM写真または図4(a)および(b)に示すTEM写真に見られるように、外径15〜100nmの炭素繊維構造体から構成される3次元ネットワーク状の炭素繊維構造体であって、前記炭素繊維構造体は、前記炭素繊維が複数延出する態様で、当該炭素繊維を互いに結合する粒状部を有するものである。 Such a carbon fiber structure is composed of a carbon fiber structure having an outer diameter of 15 to 100 nm as seen in the SEM photograph shown in FIG. 3 or the TEM pictures shown in FIGS. 4 (a) and 4 (b), for example. The carbon fiber structure is a three-dimensional network-like carbon fiber structure, and the carbon fiber structure has a granular portion that binds the carbon fibers to each other in a manner in which a plurality of the carbon fibers extend.
炭素繊維構造体を構成する炭素繊維の外径を、好ましくは15〜100nmの範囲のものとするのは、外径がこの範囲にある炭素繊維を、樹脂等のマトリックスへ改質剤、添加剤として使用した場合、高い導電性が得られるためである。この外径範囲のもので、筒状のグラフェンシートが軸直角方向に積層したもの、すなわち多層であるものは、曲がりにくく、弾性、すなわち変形後も元の形状に戻ろうとする性質が付与されるため、炭素繊維構造体が一旦圧縮された後においても、樹脂等のマトリックスに配された後において、疎な構造を採りやすくなる。 The outer diameter of the carbon fiber constituting the carbon fiber structure is preferably in the range of 15 to 100 nm because the carbon fiber having the outer diameter in this range is converted into a matrix such as a resin, a modifier, an additive. This is because high electrical conductivity can be obtained when used as . In this outer diameter range, a cylindrical graphene sheet laminated in a direction perpendicular to the axis, that is, a multilayer, is not easily bent, and is elastic, that is, has the property of returning to its original shape even after deformation. Therefore, even after the carbon fiber structure is once compressed, it is easy to adopt a sparse structure after being arranged in a matrix such as a resin.
なお、2400℃以上でアニール処理すると、積層したグラフェンシートの面間隔が狭まり真密度が1.89g/cm3から2.1g/cm3に増加するとともに、炭素繊維の軸直交断面が多角形状となる。この構造の炭素繊維は、積層方向および炭素繊維を構成する筒状のグラフェンシートの面方向の両方において緻密で欠陥の少ないものとなるため、曲げ剛性(EI)が向上する。 Incidentally, when annealing at 2400 ° C. or higher, with a true density narrowed spacing of graphene sheets stacked is increased from 1.89 g / cm 3 to 2.1 g / cm 3, and perpendicular to the axis the cross-section of the carbon fiber is polygonal that Do not. Since the carbon fiber having this structure is dense and has few defects in both the stacking direction and the surface direction of the cylindrical graphene sheet constituting the carbon fiber, the bending rigidity (EI) is improved.
加えて、該微細炭素繊維は、その外径が軸方向に沿って変化するものであることが望ましい。このように炭素繊維の外径が軸方向に沿って一定でなく、変化するものであると、樹脂等のマトリックス中において当該炭素繊維に一種のアンカー効果が生じるものと思われ、マトリックス中における移動が生じにくく分散安定性が高まるものとなる。 In addition, it is desirable that the fine carbon fiber has an outer diameter that changes along the axial direction. If the outer diameter of the carbon fiber is not constant along the axial direction and varies, it is considered that a kind of anchoring effect occurs in the carbon fiber in the matrix such as resin, and the movement in the matrix Is less likely to occur and the dispersion stability is increased.
そして、このような炭素繊維構造体においては、このような所定外径を有する微細炭素繊維が3次元ネットワーク状に存在するが、これら炭素繊維は、当該炭素繊維の成長過程において形成された粒状部において互いに結合され、該粒状部から前記炭素繊維が複数延出する形状を呈しているものである。このように、微細炭素繊維同士が単に絡合しているものではなく、粒状部において相互に強固に結合されているものであることから、樹脂等のマトリックス中に配した場合に当該構造体が炭素繊維単体として分散されることなく、嵩高な構造体のままマトリックス中に分散配合させることができる。また、このような炭素繊維構造体においては、当該炭素繊維の成長過程において形成された粒状部によって炭素繊維同士が互いに結合されていることから、その構造体自体の電気的特性等も非常に優れたものであり、例えば、一定圧縮密度において測定した電気抵抗値は、微細炭素繊維の単なる絡合体、あるいは微細炭素繊維同士の接合点を当該炭素繊維合成後に炭素質物質ないしその炭化物によって付着させてなる構造体等の値と比較して、非常に低い値を示し、マトリックス中に分散配合された場合に、良好な導電パスを形成することができる。 In such a carbon fiber structure, fine carbon fibers having such a predetermined outer diameter are present in a three-dimensional network, and these carbon fibers are formed by granular portions formed during the growth process of the carbon fibers. Are bonded to each other, and a plurality of the carbon fibers extend from the granular portion. In this way, the fine carbon fibers are not simply entangled with each other, but are firmly bonded to each other in the granular portion, so that when the structure is disposed in a matrix such as a resin, the structure is without being dispersed as carbon fibers alone can Rukoto dispersed formulated to remain in a matrix of bulky structure. Further, in such a carbon fiber structure, since the carbon fibers are bonded to each other by the granular part formed in the growth process of the carbon fiber, the electrical characteristics of the structure itself are very excellent. For example, the electrical resistance value measured at a constant compression density is obtained by attaching a simple entangled body of fine carbon fibers or a joining point between fine carbon fibers by a carbonaceous material or a carbide thereof after the synthesis of the carbon fiber. made in comparison with the value of the structure such as a very low value, when dispersed formulated into the matrix, can it to form good conductive paths.
さらに、特に限定されるわけではないが、この粒状部の粒径は、図2に示すように、前記微細炭素繊維の外径よりも大きいことが望ましい。このように炭素繊維相互の結合点である粒状部の粒径が十分に大きなものであると、当該粒状部より延出する炭素繊維に対して高い結合力がもたらされ、樹脂等のマトリックス中に当該炭素繊維構造体の集合体である微細炭素繊維集合体を配した場合に、ある程度のせん断力を加えても、3次元ネットワーク構造を保持したままマトリックス中に分散させることができる。なお、本明細書でいう「粒状部の粒径」とは、炭素繊維相互の結合点である粒状部を1つの粒子とみなして測定した値である。 Further, although not particularly limited, it is desirable that the particle size of the granular portion is larger than the outer diameter of the fine carbon fiber as shown in FIG. Thus, if the particle size of the granular part, which is the bonding point between the carbon fibers, is sufficiently large, a high bonding force is brought about to the carbon fiber extending from the granular part, and the resin is in a matrix such as a resin. the when arranged aggregates in which the fine carbon fiber aggregate of the carbon fiber structure, strong point pressure some shear force can also be dispersed to remain in the matrix holding the three-dimensional network structure. The “particle size of the granular part” in the present specification is a value measured by regarding the granular part, which is a bonding point between carbon fibers, as one particle.
さらに、(a)成分として使用される微細炭素繊維集合体における炭素繊維構造体は、3次元ネットワーク状に存在する炭素繊維が粒状部において互いに結合され、該粒状部から前記炭素繊維が複数延出する形状を呈しており、このため当該構造体は炭素繊維が疎に存在した嵩高な構造を有するが、具体的には、例えば、(a)成分の嵩密度が0.0001〜0.05g/cm3、より好ましくは0.001〜0.02g/cm3であることが望ましい。嵩密度が0.05g/cm3以下の場合、少量添加によって、樹脂等のマトリックスの物性を改善することができるため好ましい。 Further, in the carbon fiber structure in the fine carbon fiber aggregate used as the component (a), carbon fibers existing in a three-dimensional network are bonded to each other in the granular portion, and a plurality of the carbon fibers extend from the granular portion. Therefore, the structure has a bulky structure in which carbon fibers are sparsely present. Specifically, for example, the bulk density of the component (a) is 0.0001 to 0.05 g / It is desirable that it is cm 3 , more preferably 0.001 to 0.02 g / cm 3 . Bulk density of 0.05 g / cm 3 or less cases, by adding a small amount, preferably possible to improve the physical properties of the matrix such as resin.
また、(a)成分として使用される微細炭素繊維集合体における炭素繊維構造体は、3次元ネットワーク状に存在する炭素繊維がその成長過程において形成された粒状部において互いに結合されていることから、上記のように構造体自体の電気的特性等も非常に優れたものであるが、例えば、一定圧縮密度0.8g/cm3において測定した粉体抵抗値が、0.02Ω・cm以下、より望ましくは、0.001〜0.010Ω・cmであることが好ましい。粉体抵抗値が0.02Ω・cm以下の場合、樹脂等のマトリックスに配合された際に、良好な導電パスを形成することができるため好ましい。 Moreover, since the carbon fiber structure in the fine carbon fiber aggregate used as the component (a) is bonded to each other in the granular part formed in the growth process, the carbon fibers existing in a three-dimensional network form are As described above , the electrical characteristics of the structure itself are very excellent. For example, the powder resistance value measured at a constant compression density of 0.8 g / cm 3 is 0.02 Ω · cm or less. Desirably, it is preferably 0.001 to 0.010 Ω · cm. When the powder resistance is blended 0.02 ohm · cm or less in case, to a matrix such as resin is preferable because it is possible to form good electrically conductive paths.
さらに、(a)成分の酸化温度は、750℃以上であることが好ましい。前記のように炭素繊維構造体において欠陥が少なく、かつ炭素繊維が所期の外形を有するものであることから、このような高い熱安定性を有するものとなる。 Furthermore, the oxidation temperature of the component (a) is preferably 750 ° C. or higher. Few defects in the carbon fibrous structure as described above, and since the carbon fiber is one having the desired external shape, and having such a high thermal stability.
また、(a)成分として使用される微細炭素繊維集合体は、高い強度および導電性を有する上から、炭素繊維を構成するグラフェンシート中における欠陥が少ないことが望ましく、具体的には、例えば、ラマン分光分析法で測定されるID/IG比が、0.2以下、より好ましくは0.1以下であることが望ましい。ここで、ラマン分光分析では、大きな単結晶の黒鉛では1580cm-1付近のピーク(Gバンド)しか現れない。結晶が有限の微小サイズであることや格子欠陥により、1360cm-1付近にピーク(Dバンド)が出現する。このため、DバンドとGバンドの強度比(R=I1360/I1580=ID/IG)が上記のように所定値以下であると、グラフェンシート中における欠陥量が少ないことが認められるためである。 In addition, the fine carbon fiber aggregate used as the component (a) preferably has few defects in the graphene sheet constituting the carbon fiber from the viewpoint of having high strength and conductivity. Specifically, for example, It is desirable that the ID / IG ratio measured by Raman spectroscopy is 0.2 or less, more preferably 0.1 or less. Here, in the Raman spectroscopic analysis, only a peak (G band) near 1580 cm −1 appears in large single crystal graphite. A peak (D band) appears in the vicinity of 1360 cm −1 due to the fact that the crystal has a finite minute size and lattice defects. For this reason, when the intensity ratio (R = I 1360 / I 1580 = I D / I G ) of the D band and the G band is not more than the predetermined value as described above , it is recognized that the amount of defects in the graphene sheet is small. Because.
上記のような所期の形状を有する炭素繊維構造体の集合体である微細炭素繊維集合体((a)成分)は、特に限定されるものではないが、例えば、次のようにして調製することができる。 The above-mentioned desired aggregate in which fine carbon fiber aggregates of the carbon fiber structure having a shape ((a) component), is not particularly limited, for example, be prepared as follows be able to.
基本的には、遷移金属超微粒子を触媒として炭化水素等の有機化合物をCVD法で化学熱分解して炭素繊維集合体(以下、中間体という)を得、これをさらに高温熱処理(アニール)する。 Basically, organic compounds such as hydrocarbons are chemically pyrolyzed by CVD using transition metal ultrafine particles as a catalyst to obtain a carbon fiber aggregate (hereinafter referred to as an intermediate), which is further subjected to high-temperature heat treatment (annealing). .
原料有機化合物としては、ベンゼン、トルエン、キシレンなどの炭化水素、一酸化炭素(CO)、エタノール等のアルコール類などが使用できる。特に限定されるわけではないが、本発明に係る微細炭素繊維集合体を得る上においては、炭素源として、分解温度の異なる少なくとも2つ以上の炭素化合物を用いることが好ましい。なお、本明細書において述べる「少なくとも2つ以上の炭素化合物」とは、必ずしも原料有機化合物として2種以上のものを使用するというものではなく、原料有機化合物としては1種のものを使用した場合であっても、微細炭素繊維集合体の合成反応過程において、例えば、トルエンやキシレンの水素脱アルキル化(hydrodealkylation)などのような反応を生じて、その後の熱分解反応系においては分解温度の異なる2つ以上の炭素化合物となっているような態様も含むものである。雰囲気ガスには、アルゴン、ヘリウム、キセノン等の不活性ガスや水素を用いることができる。 As the raw material organic compound, hydrocarbons such as benzene, toluene and xylene, alcohols such as carbon monoxide (CO) and ethanol can be used. Although not particularly limited, in obtaining the fine carbon fiber aggregate according to the present invention, it is preferable to use at least two or more carbon compounds having different decomposition temperatures as the carbon source. The “at least two or more carbon compounds” described in the present specification does not necessarily mean that two or more kinds of raw material organic compounds are used, and one kind of raw material organic compound is used. However, in the process of synthesizing the fine carbon fiber aggregate, for example, a reaction such as hydrodealkylation of toluene or xylene occurs, and the decomposition temperature is different in the subsequent thermal decomposition reaction system. The embodiment including two or more carbon compounds is also included. As the atmospheric gas, an inert gas such as argon, helium, xenon, or hydrogen can be used.
また、触媒としては、鉄、コバルト、モリブデンなどの遷移金属あるいはフェロセン、酢酸金属塩などの遷移金属化合物と硫黄あるいはチオフェン、硫化鉄などの硫黄化合物の混合物を使用する。 As the catalyst, a transition metal such as iron, cobalt or molybdenum, or a mixture of a transition metal compound such as ferrocene or metal acetate and sulfur or a sulfur compound such as thiophene or iron sulfide is used.
第一中間体の合成は、通常行われている炭化水素等のCVD法を用い、原料となる炭化水素および触媒の混合液を蒸発させ、水素ガス等をキャリアガスとして反応炉内に導入し、800〜1300℃の温度で熱分解する。これにより、外径が15〜100nmの炭素繊維相互が、前記触媒の粒子を核として成長した粒状体によって結合した疎な三次元構造を有する炭素繊維構造体(第一中間体)が複数集まった数cmから数十cmの大きさの集合体を合成する。 The synthesis of the first intermediate is carried out by using a CVD method such as hydrocarbon that is normally performed, evaporating the mixture of hydrocarbon and catalyst as raw materials, introducing hydrogen gas or the like into the reactor as a carrier gas, Pyrolysis at a temperature of 800-1300 ° C. As a result, a plurality of carbon fiber structures (first intermediates) having a sparse three-dimensional structure in which carbon fibers having an outer diameter of 15 to 100 nm are bonded together by granular materials grown using the catalyst particles as nuclei. An assembly having a size of several centimeters to several tens of centimeters is synthesized.
原料となる炭化水素の熱分解反応は、主として触媒粒子ないしこれを核として成長した粒状体表面において生じ、分解によって生じた炭素の再結晶化が当該触媒粒子ないし粒状体より一定方向に進むことで、微細炭素状に成長する。しかしながら、本発明に係る炭素繊維構造体の集合体を得る上においては、このような熱分解速度と成長速度とのバランスを意図的に変化させる、例えば上記のように炭素源として分解温度の異なる少なくとも2つ以上の炭素化合物を用いることで、一次元的方向にのみ炭素物質を成長させることなく、粒状体を中心として三次元的に炭素物質を成長させる。もちろん、このような三次元的な炭素繊維の成長は、熱分解速度と成長速度とのバランスにのみ依存するものではなく、触媒粒子の結晶面選択性、反応炉内における滞留時間、炉内温度分布等によっても影響を受け、また、前記熱分解反応と成長速度とのバランスは、上記のような炭素源の種類のみならず、反応温度およびガス温度等によっても影響を受けるが、概して、上記のような熱分解速度よりも成長速度の方が速いと、炭素物質は繊維状に成長し、一方、成長速度よりも熱分解速度の方が速いと、炭素物質は触媒粒子の周面方向に成長する。従って、熱分解速度と成長速度とのバランスを意図的に変化させることで、上記のような炭素物質の成長方向を一定方向とすることなく、制御下に多方向として、本発明に係るような三次元構造を形成することができるものである。なお、生成する中間体において、繊維相互が粒状体により結合された前記のような三次元構造を容易に形成する上では、触媒等の組成、反応炉内における滞留時間、反応温度、およびガス温度等を最適化することが望ましい。 The thermal cracking reaction of the hydrocarbon as a raw material mainly occurs on the surface of the granular particles grown using the catalyst particles or the core, and the recrystallization of carbon generated by the decomposition proceeds in a certain direction from the catalytic particles or granular materials. , Grows in the form of fine carbon. However, in obtaining the aggregate of carbon fiber structures according to the present invention, the balance between the thermal decomposition rate and the growth rate is changed intentionally, for example, as described above , the decomposition temperature is different as a carbon source. By using at least two or more carbon compounds, the carbon material is grown three-dimensionally around the granular material without growing the carbon material only in a one-dimensional direction. Of course, the growth of such three-dimensional carbon fibers does not depend only on the balance between the thermal decomposition rate and the growth rate, but the crystal surface selectivity of the catalyst particles, the residence time in the reactor, and the furnace temperature. affected by distribution, etc., also, the balance between the decomposition rate and the growing rate is not only the type of carbon sources mentioned above, but also influenced by the reaction temperature, and gas temperatures, the When the growth rate is faster than the pyrolysis rate, the carbon material grows in the form of fibers, whereas when the growth rate is faster than the growth rate, the carbon material moves in the circumferential direction of the catalyst particles. grow up. Therefore, by intentionally changing the balance between the thermal decomposition rate and growth rate, without the growth direction of the carbon materials as described above with a certain direction, as multidirectional under control, such as according to the present invention A three-dimensional structure can be formed. Incidentally, in the resulting intermediate, in terms of fiber each other to easily form a three-dimensional structure such as a coupled said that the granulate, the composition of the catalyst, etc., the residence time in the reaction furnace, the reaction temperature, and the gas temperature Etc. are desirable.
触媒および炭化水素の混合ガスを800〜1300℃の範囲の一定温度で加熱生成して得られた第一中間体は、炭素原子からなるパッチ状のシート片を貼り合わせたような(生焼け状態の、不完全な)構造を有し、ラマン分光分析をすると、Dバンドが非常に大きく、欠陥が多い。また、生成した第一中間体は、未反応原料、非繊維状炭化物、タール分および触媒金属を含んでいる。 The first intermediate obtained by heating and generating a mixed gas of catalyst and hydrocarbon at a constant temperature in the range of 800 to 1300 ° C. is like a patch-like sheet piece made of carbon atoms being bonded together (in a burnt state). (Incomplete) structure, and the Raman spectroscopic analysis shows a very large D band and many defects. Moreover, the produced | generated 1st intermediate body contains an unreacted raw material, a non-fibrous carbide, a tar content, and a catalyst metal.
従って、このような第一中間体からこれら残留物を除去し、欠陥が少ない所期の微細炭素繊維集合体を得るために、適切な方法で2400〜3000℃の高温熱処理する。 Therefore, in order to remove these residues from such a first intermediate and obtain an intended fine carbon fiber aggregate with few defects, high-temperature heat treatment at 2400 to 3000 ° C. is performed by an appropriate method.
すなわち、例えば、この第一中間体を800〜1200℃で加熱して未反応原料やタール分などの揮発分を除去して得られた第二中間体を2400〜3000℃の高温でアニール処理することによって所期の構造体を調製し、同時に微細炭素繊維集合体に含まれる触媒金属を蒸発させて除去する。なお、この際、物質構造を保護するために不活性ガス雰囲気中に還元ガスや微量の一酸化炭素ガスを添加してもよい。 That is, for example, the second intermediate obtained by heating the first intermediate at 800 to 1200 ° C. to remove volatile components such as unreacted raw materials and tars is annealed at a high temperature of 2400 to 3000 ° C. Thus, the desired structure is prepared, and at the same time, the catalyst metal contained in the fine carbon fiber aggregate is evaporated and removed. At this time, a reducing gas or a small amount of carbon monoxide gas may be added to the inert gas atmosphere in order to protect the material structure.
前記第二中間体を2400〜3000℃の範囲の温度でアニール処理すると、炭素原子からなるパッチ状のシート片は、それぞれ結合して複数のグラフェンシート状の層を形成する(アニール品という)。 When the second intermediate is annealed at a temperature in the range of 2400 to 3000 ° C., the patch-like sheet pieces made of carbon atoms are bonded together to form a plurality of graphene sheet-like layers (referred to as an annealed product).
なお本発明において、上記のような粉砕方法1又は2に代表される粉砕工程に供される(a)成分としては、第一中間体を使用しても良いし、第二中間体を使用しても良いし、アニール品を使用しても良い。 In the present invention, as the component (a) is subjected to typified by pulverization process grinding method 1 or 2 as described above, may be used first intermediate, using a second intermediate Alternatively, an annealed product may be used.
通常、気流粉砕した後のものが(a)成分として使用される。 Usually, the product after airflow pulverization is used as the component (a).
なお、本発明において、各物性値は次のようにして測定される。 In the present invention, each physical property value is measured as follows.
<嵩密度の測定>
内径70mmで分散板付透明円筒に1g粉体を充填し、圧力0.1MPa、容量1.3リットルの空気を分散板下部から送り粉体を吹出し、自然沈降させる。5回吹出した時点で沈降後の粉体層の高さを測定する。このとき測定箇所は6箇所とることとし、6箇所の平均を求めた後、嵩密度を算出する。所の平均を求めた後、嵩密度を算出する。
<Measurement of bulk density>
Filled with 1g powder caliber transparent cylinder equipped with a distribution plate 70 mm, pressure 0.1 M P a, blowing the powder feed 1.3 liter in capacity was air from the lower side of the distribution plate, to settle naturally. At the time of blowing out 5 times, the height of the powder layer after settling is measured. At this time, the number of measurement points is six, and after obtaining the average of the six points, the bulk density is calculated. After obtaining the average of the places, the bulk density is calculated.
<円相当メディアン径>
炭素繊維集合体をイソプロピルアルコールに懸濁し、シスメックス株式会社製FPIA3000(フロー式粒子像分析装置)にて測定し、装置付属の解析ソフトを用い、粒子の輪郭から面積を求め円相当径に換算し、個数基準のメディアン径を求めた。
<Yen equivalent median diameter>
The carbon fiber aggregate is suspended in isopropyl alcohol, measured with FPIA3000 (flow type particle image analyzer) manufactured by Sysmex Corporation, and the area is obtained from the particle outline using the analysis software attached to the apparatus, and converted to the equivalent circle diameter. The number-based median diameter was determined.
<ラマン分光分析>
堀場ジョバンイボン製LabRam800を用い、アルゴンレーザーの514nmの波長を用いて測定する。
<Raman spectroscopy>
Using a LabRam800 manufactured by Horiba Joban Yvon, measurement is performed using a wavelength of 514 nm of an argon laser.
<酸化温度>
マックスサイエンス製TG−DTAを用い、空気を0.1リットル/分の流速で流通させながら、10℃/分の速度で昇温し、燃焼挙動を測定した。DTAの発熱ピークトップの温度を酸化温度として求める。
〔コーティング材料〕
本発明のコーティング材料は、上記の製造方法によって得られた解砕ないし粉砕された微細炭素繊維集合体と有機バインダー成分を含有するものであるが、本発明において用いられる有機バインダーとしては、常温(25℃±5℃)で液状のものであっても、固体状のものであってもよく、その用途に応じて、公知の各種のものを用いることができる。
<Oxidation temperature>
Using Max Science TG-DTA, the temperature was increased at a rate of 10 ° C./min while circulating air at a flow rate of 0.1 liter / min, and the combustion behavior was measured. The temperature at the top of the exothermic peak of DTA is determined as the oxidation temperature.
[Coating material]
The coating material of the present invention are those which contain crushed or pulverized fine carbon fiber aggregate and an organic binder component obtained by the above production method, as the organic binder used in the present invention, room temperature ( 25 ° C. ± 5 ° C.) or a liquid material, and various known materials can be used depending on the application.
具体的には、例えば、溶剤系塗料用や油性印刷インクに通常使用されているアクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アミノ樹脂、塩化ビニル樹脂、シリコーン樹脂、ガムロジン、ライムロジン等のロジン系樹脂、マレイン酸樹脂、ポリアミド樹脂、ニトロセルロース、エチレン−酢酸ビニル共重合樹脂、ロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂等のロジン変性樹脂、石油樹脂等を用いることができる。また、水系塗料用や水性インク用としては、水溶性アクリル樹脂、水溶性スチレン−マレイン酸樹脂、水溶性アルキッド樹脂、水溶性メラミン樹脂、水溶性ウレタンエマルジョン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル樹脂等を用いることができる。 Specifically, for example, acrylic resins, alkyd resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, melamine resins, amino resins, vinyl chloride resins, silicones commonly used for solvent-based paints and oil-based printing inks Resin, rosin resin such as gum rosin, lime rosin, maleic acid resin, polyamide resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, rosin modified phenolic resin, rosin modified resin such as rosin modified maleic resin, petroleum resin, etc. be able to. For water-based paints and water-based inks, water-soluble acrylic resins, water-soluble styrene-maleic acid resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urethane emulsion resins, water-soluble epoxy resins, water-soluble polyester resins Etc. can be used.
また、本発明に係る導電性コーティング材料中には、上記のような有機バインダー成分および炭素繊維集合体の他、必要に応じて、溶剤、油脂、消泡剤、染料および顔料ないし体質顔料等の着色剤、乾燥促進剤、界面活性剤、硬化促進剤、助剤、可塑剤、滑剤、酸化防止剤、紫外線吸収剤、各種安定剤等の添加剤が配合され得る。 Further, the conductive coating material according to the present invention, other organic binder component and carbon fiber aggregates such as described above, if necessary, solvent, oil, defoamers, such as dyes and pigments or extender pigments Additives such as colorants, drying accelerators, surfactants, curing accelerators, auxiliaries, plasticizers, lubricants, antioxidants, ultraviolet absorbers, and various stabilizers may be blended.
溶剤としては、溶剤系塗料ないしインク用に通常使用されている大豆油、トルエン、キシレン、シンナー、ブチルアセテート、メチルアセテート、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶剤、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素系溶剤、シクロヘキサン等の脂環族炭化水素系溶剤、ミネラルスピリット等の石油系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、脂肪族炭化水素等を用いることができる。 Solvents include soybean oil, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether commonly used for solvent-based paints or inks. Such as glycol ether solvents such as ethyl acetate, butyl acetate and amyl acetate, aliphatic hydrocarbon solvents such as hexane, heptane and octane, alicyclic hydrocarbon solvents such as cyclohexane, mineral spirits, etc. Petroleum solvents, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, aliphatic hydrocarbons, and the like can be used.
また水系塗料用溶剤としては、水系塗料ないしインク用に通常使用されている、水と、エチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ等のグリコールエーテル系溶剤、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のオキシエチレン又はオキシプロピレン付加重合体、エチレングリコール、プロピレングリコール、1,2,6−ヘキサントリオール等のアルキレングリコール、グリセリン、2−ピロリドン等の水溶性有機溶剤とを混合して使用することができる。 Water-based paint solvents include water and alcohol solvents such as ethyl alcohol, propyl alcohol, and butyl alcohol, and glycols such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve that are commonly used for water-based paints and inks. Ether solvents, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other oxyethylene or oxypropylene addition polymers, ethylene glycol, propylene glycol, 1,2,6-hexanetriol, etc. It can be used by mixing with a water-soluble organic solvent such as alkylene glycol, glycerin, 2-pyrrolidone and the like.
油脂としては、あまに油、きり油、オイチシカ油、サフラワー油等の乾性油を加工したボイル油を用いることができる。 As oils and fats, boil oils obtained by processing dry oils such as linseed oil, persimmon oil, sea lion oil, safflower oil and the like can be used.
消泡剤、着色剤、乾燥促進剤、界面活性剤、硬化促進剤、助剤界可塑剤、滑剤、酸化防止剤、紫外線吸収剤、各種安定剤等等としても、従来、これらの導電性コーティング材料において、用いられている公知の各種のものを用いることができる。 Conventionally, these conductive coatings have also been used as antifoaming agents, coloring agents, drying accelerators, surfactants, curing accelerators, auxiliary agent plasticizers, lubricants, antioxidants, UV absorbers, various stabilizers, and the like. Various known materials used can be used as the material.
本発明のコーティング材料は、前記のような有機バインダー成分と共に、前述の微細炭素繊維集合体を含有する。微細炭素繊維集合体の含有量は、コーティング材料の用途や有機バインダー成分の種類等によって異なるが、好ましくはコーティング材中0.01〜50質量%である。
本発明のコーティング材料の調製方法としては、湿式あるいは乾式の各種の混合方法を用いることができる。また、得られる導電性コーティング材料の品質安定性をさらに向上させるために、遠心処理やフィルター処理を施し、粗大粒子を除去する工程を設けても良い。
The coating material of the present invention contains the above-mentioned fine carbon fiber aggregate together with the organic binder component as described above. The content of the fine carbon fiber aggregate varies depending on the use of the coating material, the type of the organic binder component, and the like, but is preferably 0.01 to 50% by mass in the coating material .
As a method for preparing the coating material of the present invention, various wet or dry mixing methods can be used. Moreover, in order to further improve the quality stability of the obtained conductive coating material, a step of removing coarse particles by performing a centrifugal treatment or a filter treatment may be provided.
以下、本発明を実施例に基づき、より具体的に説明する。
(合成例1)
CVD法によって、トルエンを原料として微細炭素繊維構造体の集合体を合成した。
Hereinafter, the present invention will be described more specifically based on examples.
(Synthesis Example 1)
An aggregate of fine carbon fiber structures was synthesized by CVD using toluene as a raw material.
触媒としてフェロセン及びチオフェンの混合物を使用し、水素ガスの還元雰囲気で行った。トルエン、触媒を水素ガスとともに380℃に加熱し、生成炉に供給し、1300℃で熱分解して、微細炭素繊維構造体(第一中間体)の集合体を得た。この第一中間体をトルエン中に分散して電子顕微鏡用試料調製後に観察したSEMおよびTEM写真を図1及び2に示す。 A mixture of ferrocene and thiophene was used as a catalyst, and the reaction was performed in a hydrogen gas reducing atmosphere. Toluene and the catalyst were heated to 380 ° C. together with hydrogen gas, supplied to the production furnace, and thermally decomposed at 1300 ° C. to obtain an aggregate of fine carbon fiber structures (first intermediate). FIGS. 1 and 2 show SEM and TEM photographs observed after the first intermediate was dispersed in toluene and the sample for the electron microscope was prepared.
合成された第一中間体を窒素中で900℃で焼成して、タールなど分離し、第二中間体を得た。 The synthesized first intermediate was calcined at 900 ° C. in nitrogen to separate tar and the like to obtain a second intermediate.
さらにこの第二中間体をアルゴン中で2600℃で高温熱処理し、得られた炭素繊維構造体の集合体を気流粉砕機にて粉砕し、炭素繊維構造体の集合体(アニール品)を得た。得られた炭素繊維構造体の集合体をトルエン中に超音波で分散して電子顕微鏡用試料調製後に観察したSEMおよびTEM写真を図3、4に示す。
(実施例1)
合成例1にて得られた微細炭素繊維構造体の集合体(アニール品)1.5質量部、エチレンオキシド・プロピレンブロック共重合体0.03質量部、イソプロピルアルコール100質量部を含む組成物について、キャビトロン(商標名、(株)ユーロテック製)CD1010型にて微細炭素繊維構造体の集合体を粉砕した(前記粉砕方法1)。周速を40m/秒(11,200rpm)、流速20Kg/分、回転ロータとステータとの間は距離は4mm、パス回数を30とした。
Further, this second intermediate was heat-treated at 2600 ° C. in argon at high temperature, and the aggregate of the obtained carbon fiber structure was pulverized with an airflow pulverizer to obtain an aggregate of carbon fiber structure (annealed product). . FIGS. 3 and 4 show SEM and TEM photographs of the obtained carbon fiber structure aggregate dispersed in toluene with ultrasonic waves and observed after preparing a sample for an electron microscope.
Example 1
About the composition containing 1.5 parts by mass of the aggregate (annealed product) of fine carbon fiber structures obtained in Synthesis Example 1, 0.03 parts by mass of ethylene oxide / propylene block copolymer, 100 parts by mass of isopropyl alcohol, Aggregates of fine carbon fiber structures were pulverized with Cavitron (trade name, manufactured by Eurotech Co., Ltd.) CD1010 type (the pulverization method 1). The peripheral speed was 40 m / sec (11,200 rpm), the flow rate was 20 kg / min, the distance between the rotating rotor and the stator was 4 mm, and the number of passes was 30.
得られた組成物からイソピロピルアルコールとエチレンオキシド・プロピレンブロック共重合体を除去して得られた微細炭素繊維構造体の集合体の物性値を表1に示した。メディアン径が比較例1と比べて小さいことから、微細炭素繊維構造体の集合体は粉砕されており、酸化温度及びID/IG値が比較例1と同じ程度であることから、本発明の所望の粉砕が行なわれていることを確認した。
(実施例2)
合成例1にて得られた微細炭素繊維構造体の集合体(アニール品)1.5質量部、エチレンオキシド・プロピレンブロック共重合体0.03質量部、イソプロピルアルコール100質量部を含む組成物について、アルティマイザー(商標名、(株)スギノマシン製)HJP−25080型にて凝集体を粉砕した(前記粉砕方法2)。ノズルの圧力を150MPa、流速を520m/秒、パス回数を5とした。
Table 1 shows physical property values of aggregates of fine carbon fiber structures obtained by removing isopropyl alcohol and ethylene oxide / propylene block copolymer from the obtained composition. Since the median diameter is smaller than that of Comparative Example 1, the aggregate of fine carbon fiber structures is pulverized, and the oxidation temperature and I D / IG value are the same as those of Comparative Example 1. It was confirmed that the desired pulverization was performed.
(Example 2)
About the composition containing 1.5 parts by mass of the aggregate (annealed product) of fine carbon fiber structures obtained in Synthesis Example 1, 0.03 parts by mass of ethylene oxide / propylene block copolymer, 100 parts by mass of isopropyl alcohol, The agglomerates were pulverized with an optimizer (trade name, manufactured by Sugino Machine Co., Ltd.) HJP-25080 (the pulverization method 2). The nozzle pressure was 150 MPa, the flow rate was 520 m / sec, and the number of passes was 5.
得られた組成物からイソプロピルアルコールを除去して得られた微細炭素繊維構造体の集合体の物性値を表1に示した。メディアン径が比較例1と比べて小さいことから、微細炭素繊維集合体は粉砕されており、酸化開始温度及びID/IG値が比較例1と同じ程度であることから、本発明の所望の粉砕が行なわれていることを確認した。
(比較例1)
合成例1にて得られた微細炭素繊維構造体の集合体(アニール品)の物性値を表1に示した。
(比較例2)
合成例1にて得られた微細炭素繊維構造体の集合体(アニール品)1.5質量部、エチレンオキシド・プロピレンブロック共重合体0.03質量部、イソプロピルアルコール100質量部を含む組成物について、ウルトラアペックスミル(商標名、寿工業(株)製)UAM05型(ビーズミル、ビーズ径0.1mm)にて微細炭素繊維構造体の集合体を粉砕した。周速を10m/秒(2940rpm)、パス回数を7とした。
Table 1 shows physical property values of aggregates of fine carbon fiber structures obtained by removing isopropyl alcohol from the obtained composition. Since the median diameter is smaller than that of Comparative Example 1, the fine carbon fiber aggregate is pulverized, and the oxidation initiation temperature and the I D / IG value are the same as those of Comparative Example 1. It was confirmed that the pulverization was performed.
(Comparative Example 1)
Table 1 shows the physical property values of the aggregate (annealed product) of the fine carbon fiber structure obtained in Synthesis Example 1.
(Comparative Example 2)
About the composition containing 1.5 parts by mass of the aggregate (annealed product) of fine carbon fiber structures obtained in Synthesis Example 1, 0.03 parts by mass of ethylene oxide / propylene block copolymer, 100 parts by mass of isopropyl alcohol, The aggregate of fine carbon fiber structures was pulverized with an Ultra Apex mill (trade name, manufactured by Kotobuki Industries Co., Ltd.) UAM05 type (bead mill, bead diameter 0.1 mm). The peripheral speed was 10 m / sec (2940 rpm) and the number of passes was 7.
得られた組成物からイソプロピルアルコールを除去して得られた炭素繊維構造体の集合体の物性値を表1に示した。メディアン径が比較例1と比べて小さいことから、微細炭素繊維構造体の集合体は粉砕されているが、比較例1と比べて酸化温度が低下し、ID/IG値が大きくなっていることから、この粉砕方法において微細炭素繊維構造体の集合体が損傷を受けていることが分かった。
(比較例3)
合成例1にて得られた微細炭素繊維構造体の集合体(アニール品)1.5質量部、エチレンオキシド・プロピレンブロック共重合体0.02質量部、イソプロピルアルコール100質量部を含む組成物について、OBミル(商標名、ターボ工業(株)製)OB0.5型(ビーズミル、ビーズ径0.8mm)にて微細炭素繊維構造体の集合体を粉砕した。周速を23m/秒(2800rpm)、パス回数を9とした。以下、実施例1と同様の操作を行い、得られた微細炭素繊維構造体の集合体の物性値を表1に示した。メディアン径が比較例1と比べて小さいことから、微細炭素繊維構造体の集合体は粉砕されているが、比較例1と比べて酸化温度が低下し、ID/IG値が大きくなっていることから、この粉砕方法において微細炭素繊維構造体の集合体が損傷を受けていることが分かった。
Table 1 shows physical property values of aggregates of carbon fiber structures obtained by removing isopropyl alcohol from the obtained composition. Since the median diameter is smaller than that of Comparative Example 1, the aggregate of the fine carbon fiber structure is pulverized, but the oxidation temperature is lowered and I D / IG value is increased as compared with Comparative Example 1. From this, it was found that the aggregate of fine carbon fiber structures was damaged in this pulverization method.
(Comparative Example 3)
About the composition containing 1.5 parts by mass of the aggregate (annealed product) of fine carbon fiber structures obtained in Synthesis Example 1, 0.02 parts by mass of ethylene oxide / propylene block copolymer, 100 parts by mass of isopropyl alcohol, The aggregate of fine carbon fiber structures was pulverized with an OB mill (trade name, manufactured by Turbo Industry Co., Ltd.) OB0.5 type (bead mill, bead diameter 0.8 mm). The peripheral speed was 23 m / sec (2800 rpm), and the number of passes was 9. Hereinafter, the same operations as in Example 1 were performed, and the physical property values of the obtained aggregate of fine carbon fiber structures are shown in Table 1. Since the median diameter is smaller than that of Comparative Example 1, the aggregate of the fine carbon fiber structure is pulverized, but the oxidation temperature is lowered and I D / IG value is increased as compared with Comparative Example 1. From this, it was found that the aggregate of fine carbon fiber structures was damaged in this pulverization method.
実施例1で得られた微細炭素繊維構造体の集合体の含有量が1質量%となるように、微細炭素繊維構造体の集合体を、エポキシ樹脂(アデカレジン EP4100E、エポキシ当量190、旭電化工業(株)製)、硬化剤(アデカハードナーEH3636−AS、旭電化工業(株)製)に配合し、10分混練し、コーティング材料を調製した。
The aggregate of the fine carbon fiber structure was treated with an epoxy resin (Adeka Resin EP4100E, epoxy equivalent 190, Asahi Denka Kogyo Co., Ltd.) so that the content of the aggregate of the fine carbon fiber structure obtained in Example 1 was 1% by mass. Ltd.), a curing agent (ADEKA hARDENER EH3636-AS, manufactured by Asahi Denka Co., Ltd. blended to Ltd.), and 10 minutes mixing kneaded, and the coating material was prepared.
このコーティング材料を200μmのギャップでドクターブレードを用いて製膜した。170℃で30分硬化後、塗膜の中の微細炭素繊維構造体の集合体に起因する凝集体を目視観察した。炭素繊維構造体の集合体に起因する凝集体は殆ど観察されなかった。
(実施例4)
実施例2で得られた微細炭素繊維構造体の集合体の含有量が1質量%となるように、炭素繊維構造体の集合体を、エポキシ樹脂(アデカレジンEP4100E、エポキシ当量190、旭電化工業(株)製)、硬化剤(アデカハードナーEH3636−AS、旭電化工業(株)製)に配合し、10分混練し、コーティング材料を調製した。
This coating material was formed into a film using a doctor blade with a gap of 200 μm. After curing at 170 ° C. for 30 minutes, the aggregate due to the aggregate of fine carbon fiber structures in the coating film was visually observed. The aggregate resulting from the aggregate | assembly of a carbon fiber structure was hardly observed.
Example 4
The aggregate of the carbon fiber structures was prepared from an epoxy resin (Adeka Resin EP4100E, epoxy equivalent 190, Asahi Denka Kogyo Co., Ltd.) so that the content of the aggregate of fine carbon fiber structures obtained in Example 2 was 1% by mass. Ltd.)), a curing agent (ADEKA hARDENER EH3636-AS, formulated in Asahi Denka Co., Ltd.), and 10 minutes mixing kneaded, and the coating material was prepared.
このコーティング材料を200μmのギャップでドクターブレードを用いて製膜した。170℃で30分硬化後、塗膜の中の微細炭素繊維構造体の集合体に起因する凝集体を目視観察した。炭素繊維構造体の集合体に起因する凝集体は殆ど観察されなかった。
(比較例4)
比較例1で得られた微細炭素繊維構造体の集合体の含有量が1質量%となるように、微細炭素繊維構造体の集合体を、エポキシ樹脂(アデカレジンEP4100E、エポキシ当量190、旭電化工業(株)製)、硬化剤(アデカハードナーEH3636−AS、旭電化工業(株)製)に配合し、10分混練し、コーティング材料を調製した。
This coating material was formed into a film using a doctor blade with a gap of 200 μm. After curing at 170 ° C. for 30 minutes, the aggregate due to the aggregate of fine carbon fiber structures in the coating film was visually observed. The aggregate resulting from the aggregate | assembly of a carbon fiber structure was hardly observed.
(Comparative Example 4)
The aggregate of the fine carbon fiber structure was treated with an epoxy resin (Adeka Resin EP4100E, epoxy equivalent 190, Asahi Denka Kogyo Co., Ltd.) so that the content of the aggregate of the fine carbon fiber structure obtained in Comparative Example 1 was 1% by mass. Ltd.), a curing agent (ADEKA hARDENER EH3636-AS, manufactured by Asahi Denka Co., Ltd. blended to Ltd.), and 10 minutes mixing kneaded, and the coating material was prepared.
このコーティング材料を200μmのギャップでドクターブレードを用いて製膜した。170℃で30分硬化後、塗膜の中の炭素繊維凝集体を目視観察した。微細炭素繊維構造体の集合体に起因する多数の凝集体が観察された。 This coating material was formed into a film using a doctor blade with a gap of 200 μm. After curing at 170 ° C. for 30 minutes, the carbon fiber aggregates in the coating film were visually observed. Numerous aggregates due to aggregates of fine carbon fiber structures were observed.
1 ロータ
2 ステータ
3 ギャップ
4 ノズル
5 チャンバ中央部
1 Rotor 2 Stator 3 Gap 4 Nozzle 5 Center of chamber
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JP2006021873A JP4908858B2 (en) | 2006-01-31 | 2006-01-31 | Method for producing fine carbon fiber aggregate |
PCT/JP2007/051390 WO2007088810A1 (en) | 2006-01-31 | 2007-01-29 | Process for producing fine carbon fiber agglomerate |
US12/162,950 US20090023853A1 (en) | 2006-01-31 | 2007-01-29 | Method for manufacturing aggregates of fine carbon fibers |
EP07707621A EP1980656A4 (en) | 2006-01-31 | 2007-01-29 | Process for producing fine carbon fiber agglomerate |
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EP (1) | EP1980656A4 (en) |
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JP2010013742A (en) * | 2008-07-01 | 2010-01-21 | Teijin Ltd | Method for producing ultrafine carbon fiber |
KR20110027752A (en) * | 2008-07-04 | 2011-03-16 | 호도가야 가가쿠 고교 가부시키가이샤 | Carbon fiber and composite material |
KR101400507B1 (en) * | 2011-12-21 | 2014-05-30 | 오씨아이 주식회사 | Dispersion Method of Carbonous Fibers Using In-line Dispersion Method and Manufacturing Method of Carbon Composites thereof |
US9103803B2 (en) | 2012-10-10 | 2015-08-11 | Empire Technology Development Llc | Defect detection in saturable absorbers |
JP7077706B2 (en) * | 2018-03-27 | 2022-05-31 | 日本ゼオン株式会社 | Method for manufacturing fibrous carbon nanostructure dispersion |
US12053908B2 (en) | 2021-02-01 | 2024-08-06 | Regen Fiber, Llc | Method and system for recycling wind turbine blades |
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JPH0735251B2 (en) | 1986-07-14 | 1995-04-19 | 昭和電工株式会社 | Graphite fine powder |
JPS6465144A (en) | 1987-06-24 | 1989-03-10 | Yazaki Corp | Vapor-growth carbonaceous fiber and its resin composition |
JP2862578B2 (en) | 1989-08-14 | 1999-03-03 | ハイピリオン・カタリシス・インターナシヨナル・インコーポレイテツド | Resin composition |
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US5591382A (en) * | 1993-03-31 | 1997-01-07 | Hyperion Catalysis International Inc. | High strength conductive polymers |
US6011098A (en) * | 1993-04-26 | 2000-01-04 | Canon Kabushiki Kaisha | Water-based ink |
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JP4362276B2 (en) * | 2001-11-07 | 2009-11-11 | 昭和電工株式会社 | Fine carbon fiber, its production method and its use |
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US20090023853A1 (en) | 2009-01-22 |
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